A process for the separation of higher fatty acid partial esters of polyhydric alcohols from mixture containing the same



.separation can generally be obtained.

Patented Aug. 26, 1952 UNITED STATES PATENT 2,608,564 OFFICE H A PROCESS FOR THE SEPARATION OF p HIGHER FATTY ACID PARTIAL ESTERS OF. POLYHYDRIC ALCOHOLS FROM.

MIXTURE CONTAINING THE SAME Harland H. Young and Howard C. Black, Chicago, 111., assignors to Swift & Company, Chicago,

111., a corporation of Illinois No Drawing. Original application December 7,

1944, Serial No. 567,126. Divided and this applicationJuly 3, 1948, Serial No. 37,083

i This invention relates to thefractionation of fatty esters and has to do more particularly'with theseparation of glycerides of higherfatty acids into fractions of varying degrees of saturation and melting point by SOIVGIltXtlBfltIHQI'It: The invention involves the purification and fractionacation to thetreatment of both animal and vegetable fats; -for-example, the: destearinating of animal fats such as white and yellow grease to produce stearine and grease oil, the purification andseparation of monoand diglycerides from mixtures of mono-, di-, and triglycerides; and the separationof glycerides from thefatty esters of higher monohydric alcohols such as occur in sperm oil.

"been the so-called seeding in which the melted fatty material is slowly chilled. The more saturated portions crystallize andare separated by a straining or pressing operation. Solvent fractionation has been proposed as a-means for separating thewmore saturated'from the less saturated. fractions, but experience has shown that l as sharp a separation as desired is not obtained. A sharp separation can be obtained if the fatty .material is dissolved in a solvent and chilled until the higher melting point constituents crystallize. The solid material is'then filtered off and Washed with fresh chilled solvent. if

By dissolving the fatty material in a solvent, ::'generally at an elevated temperature, and coolingthe'mixture gradually, a fraction precipitates which consists of the higher melting: more satuwrated constituents;

If the cooling and separation are carried out properly the fractionwhich separates-is quite uniform in degree of saturation and melting point and consists of products of quite similar chemical constitution. and physical properties Afterthe solid precipitate has been removed, further cooling of thefiltrate results =inthe separation of a further fraction which is somewhat less saturated and of slightly lower "melting point than the original precipitate. The

filtration and cooling steps may be continued to yield any number of fractions, each with different melting point and degree of saturation.

If'the process is carried out carefully, quite sharp ther degree of separation is desired, any of the 21 Claims. (01. 260-4=10.7)

properties.

fractions can be redissolved in a portion of the solvent or another solvent and rechilled andfilteredin a manner similar to the original chilling and filtering. Byrepetitionof this process fractions of high degree of uniformity andpurity can i be produced.

Polyhydric alcohol partial esters, particularly fatty acidmonoglycerides, are employed in many ways and for different purposes because of their surface activity, compatibility with numerous materials, and other desirable physical and chemical properties. In recent years many methods have been described for the preparation and use of these polyhydric alcohol partial esters. In general, however, these procedures do not produce simple mixtures of monoglycerides, but instead they usually form compositions containing in addition to the monoglycerides some diglyceridcs and triglycerides, as well as other organic and inorganic impurities. Among the methods disclosed in prior patents is that of Kapp, U. S. Patent No. 2,207,257, wherein a mixture of fatty acid mono-, di-, and triglycerides is extracted from soaps of the corresponding fatty acids. The resulting product is, as stated hereinbefore, a mixture of materials, some of which are not desired. It is an object of this invention to. prepare purer and more uniform fractions of esters of polyhydric alcohols including polyhydric alcohol partial esters.

Another object of this invention isto separate 'mixtures of fatty acid glycerides into uniform fractions, each possessing different physical-and chemical properties.

Another object of the invention is to provide an improved process for separating glyceride esters andesters of other polyhydric alcohols by fractional crystallization.

Another object of this invention is to produce relatively pure fractions of fatty acid partial esters having uniform unsaturation, solubility, stability, surface activity and other desirable An additional object is to provide an economical process for solvent-extracting fatty acid monoglycerides in order to purify said materials.

A further object of the invention is to provide improved solvents for separating fatty acid glycerides by solvent crystallization.

A further object of the invention is to produce relatively pure fractions of fatty acid partial glycerides having uniform unsaturation, solubility, stability, surface activity, and other de- If furspecies of the materia1 treated.

the dissolving of the ester material in a suitable solvent, then reducing the temperature of the solution to separate fractions of esters, and sepa rating the fractions so separated. One method is to form a solution of a mixture of esters in a crystallization solvent having a differential-solubility for the various components of the mixture, utilizing sufiiciently high temperatures to completely dissolve the oil, chilling the solution to separate the desired fraction as crystals, and then duced, the less-saturated, lower melting. point fractions begin to precipitate. By controlling the amount of solvent and the temperature, any desired number of fractions may be separated.

The present invention may be used for separating various types of glyceride fats including triglyceride, diglyceride, monoglyceride, or mixtures thereof. Also the invention can be applied to the separation of the fatty'acid esters of other polyhydric alcohols such as ethylene glycol, propylene glycol, erythritol, diet-hylene glycol and the like. These may be either completely esterified esters or partial esters. It may also be applied to separation of the fatty esters of monohydric alcohols such as occur in the common waxes; for example, beeswax and spermaceti.

The broad principles of the present invention may be applied to any of theaforementioned materials, although the specific details of the invention may have to be varied depending on the In practicing the invention it is desirable to use conditions most favorable to the particular solvent being employed. Thus the temperature and the solvent ratio may have to be varied depending onthe method of treatment. The temperature of operation will depend mainly on the type of solvent,

"the proportion of solvent, and the material under treatment. The solvents are ordinarily more s elective at lower temperatures, but the quantity of material dissolved is usually lower; hence, it is a question of balancing the degree of separation against the quantity of solvent required. In

70 F.) to about 200 F. The proportion of solvent to ester material under treatment will usually be within a range of about 1 part to 15 parts by volume of solvent to 1 part of oil. For simple single-stage crystallizations a proportion of about to 5 parts'of solvent to 1 part of ester material is satisfactory, and preferably about 1-3.

One aspect of the present invention comprises the purification and/or fractionation of partial esters of aliphatic polyhydroxy substances occurring in mixtures containing these materials by solvent extraction with a selective solvent. It has been found that when a polar solvent is con tacted with mixtures containing partial esters of aliphatic polyhydroxy substances, there is a greater tendency to dissolve the polyhydroxy substances having the lower number of ester substitutions than those more fully esterified, and the more unsaturated derivatives than the more saturated ones. B this means the applicants can extract concentrated monoglycerides from immiscible liquids at all times.

4 c mixtures containing diand triglycerides, and/or to separate monoglycerides into unsaturated and saturated fractions. The polar solvent is employed in such proportions and under such conditions that two phases are formed; one, a solution of the aliphatic polyhydroxy substances having a'larger number of free hydroxyl groups; and the other, an insoluble or at least partially immiscible phase containing some impurities and more fully esterified polyhydroxy compounds.

One method is to operate so that two liquid phases are formed; in other words, to employ liquidliquid extraction.

When employing liquid-liquid extraction it is Within the scope of this invention to employ continuous counter-current extraction (in a tower), multiple-stage counter-current extraction (mixing and settling), or one or more stages of batch extraction (mixing and settling). In any of advantageous to use one or more immiscible nonpolar solvents in conjunction with the polar solvent or solvents in order to set up an opposed solubilizing action on the more fully esterified polyhydroxy substances when using polar'materials possessing very high solvent action or when operating on mixtures of partial esterswhich have many solubilizing groups, such as olefine linkages or hydroxy radicals. It is also a feature of this invention to'employ miscible non-polar solvents or 'miscible anti-solvents along with the polar solvents in order to improve or reduce, i. e., control, the solvent properties on the materials which are not desired to be extracted. For example, water-saturated solvents are in many cases more selective than the corresponding anhydrous materials. In other cases a highly effective but nonselective miscible solvent may be added to a very selective solvent to increase the yield.

In operating this process itis possible to employ temperatures and proportions which yield This is the case in the preferred method of operating in a continuous counter-current manner. The procedure in this type of operation usually is to flow the mixture containing partial esters of polyhydric alcohols, with or without non-polar solvents, such as petroleum ether, into a vertical tower near the bottom or at any point substantially below the top thereof. Simultaneously, a polar solvent, such as furfural, is introduced into the tower near the top. If desired, the tower may be equipped with packing, baffles, plates and/or heating units to vary or control the temperature throughout the extraction. The denser solvent flows downwardly through the column counter-current to the rising mixture of aliphatic polyhydroxy derivatives. An

interface will be formed at one point in the tower between. the lower downwardly flowing solvent phase through which the partial esters rise in the form of drops or the like, andthe upper rising. extracted partial ester phase through which falls the fresh solvent. This interface is usually midway between the two in let ports but may be nearer to either of them, depending on the characteristics of the material under treatment and the extractant. It is also desirable to have a separating zone below the lower and above the upper entrance ports for the materials to be counter-currently treated in order to permit complete separation of the immiscible phases. For effecting maximum concentration it is another feature of this invention to separate the solvent from the extract and to return a portion of the extracted material to the tower at a point near the bottom but below the entrance port of the original mixture undergoing extraction. By this process of reflux it is possible to even further concentrate and purify the less highly substituted polyhydroxy partial ester. With solvents, such as alcohol, having a lower density than the oil, the oil is introduced near the top and the solvent near the bottom.

tract from each stage moves progressively toward the first stage. .the extract fromthe first stage is separated from its solvent and a substantial portion of the When employing reflux,

purified solvent-free extract of less fully esterified material is returned as the charge to the first stage. In each of these stages the raflinate from the previous stage and the extract from the following stage are intimately mixed for a substantial period. The mixture is then permitted to settle and the two layers are separately drawn off, one representing the rafllnate charge to the following stage, and the other representing extract charge to the next previous stage. The raffinate from the last stagecomprises the more fully esterifled and more saturated polyhydroxy derivatives.

Another procedure involves concurrent extrac- .tion by flowing the material to be extracted in a mixture with the polar solvent through a zone wherein the conditions are such that the materials are miscible; for example, higher temperatures and/or higher proportions of solvents. The materials are held in this condition for a sufiicient time to effect uniformity of solution; for example, by flowing through a pipe of relatively small cross-section and tortuous path. After complete mixing, the mixture is treated so that incipient stratification (turbidity) takes place; for example, by cooling the mixture, by

evaporation, or by addition of an immiscible,

non-polar solvent (e. g., hydrocarbon) or a miscible non-solvent (e. g., water). The material in this turbid state is subjected to centrifugal action in order to effect separation of the suspended matter, i. e., the material causing turbidity. This process may involve the simultaneous stratification and separation during the centrifugal treatment. It is also possible to cool or precipitate by other means to an extent that immiscible layers are formed, but the preferred procedure involves the centrifugal action because of the more rapid separation effected.

Of course, simple batch extracting ina single or a plurality of stages, each employing fresh solvent, can be used, but this is not generally employed in commercial operation because of the higher cost and poorer yields involved.

The process, as stated hereinbefore, is directed to the liquid-liquid extraction of the partial ester mixture. Such procedures may also include operations wherein a solid phase is formed in addition to the two liquid phases. In other words, a double purification is effected by separation of the three phases.

tion may be effected under conditions. that total 7 'It'. is possible, according The processes involving solid-liquid extraction may be conducted in the following manner, among other methods: 1 g

A'solid,plastic composition of partial esters may be admixed with a polar solvent at a temperature below that at which the composition becomes liquid. After the compositionrhas been intimately mixed with .the, solvent, the insoluble extracted portion is separated'by means of'contrifuging, filtering'and/or decanting. The liquid extract is treated toremove the solvent which may be returned for extracting additional composition under treatment. .The material removed from. the solvent is a fraction. .of .polyhydroxy material of lower degree of substitution. The

process may be: repeated in one or more stages :employing the same or different solvents or mixtures of solvents.

. Other methods include thecomplete dissolution of themixture in the polar solvent or solvents withlor without miscible non-polar solvents and non-solvents at higher temperatures followed by moved by. centrifuging, filtering and/or decantiing; This issimilar to a procedure outlined for liquid-liquid extraction, buttemperatures' are employed at which the separated material is solid rather'thanliquid. I J

to the invention; to remove water and dissolved salts or alkali "from the compositions containing the partial esters by means of polar solvents. The addition of a water- .immiscible polar solvent or solvent combination will cause aqueous material to separate. to. a major extentfrom the resulting :solution ofpartial esters of polyhydric alcohols" Thisfisepammiscibility of the solvent and ester, composition results or under conditions that I fractionation takeswplac'e; Non-polar. solvents in conjunction withrthe'polar solvents are also effective for this "purpose.

When employing polar solvents, miscible wholly, or partially with water, it is .possible to cause water separation by theaddition of salts of. inorganic acids or of low molecular weight organic acids such as sodium chloride; sodium sulphate, sodium phosphate, sodium carbonate. sodium borate, sodium acetate or-the corresponding ammoniumor'other alkali metal salts. An immiscible aqueous salt solution or salt layer will '55 water-soluble impurities are present these will separate out, and if. any organic salts and other probably be removedtoo. Hence the process is xnotonly one of fractionation, but also involves j simultaneous purification and extraction from other materials. y

The following examplesare given for thepurpose of illustrating the'present invention as applied to thetreatment of materials containing partial esters; but they are not intended to be limiting on the scope thereof.

Y ,Eaiainplef 1,000grarns of partially hydrogenated soybean 011,:500 grams of glycerol, and 10 grams 'of sodium .hydroxidearethoroughly mixed, heated to' the about 4'. hoursother undesirable properties. id'e fractions maybe employed separately or in ening, peanut butter, and the like.

-is.' precipitated and filtered, or otherwise separated, from the solution.

The alcoholic. solution is then slowly cooled to aboutEO" C. and maintained at this temperature for about i hours. At this temperature a small amount. of oily material will separate out below the alcoholic solution. This insoluble portion which is essentially triglyceride material is separated. The alcoholic solution is again cooled to a slightly lower temperature of about 40 C. and maintained at this temperature for about 4 hours. Another portion of oily material comprising essentially diglycerides separates out and is removed. The solution is then permitted to cool to: about 20 C. (room temperature) over night and an. insoluble product consisting essentially of crystallized monoglycerides is filtered from the solution. The filtrate is then cooled to about 2 /2 C. and maintained at this temperature for A further precipitate of monogly'cerides is formed and removed by filtration. The alcoholic solution is then-cooled to about 35 C. and a still further precipitate of monoglycerides separates out and is removed therefrom.

Thelatter three precipitates are redissolved in 2' *liters'of alcohol at a temperature of 60 C. and the solution decolorized with activated carbon. The solution is then cooled in stages as in the first series of fractional precipitations to obtain corresponding fractions of tri-, diand monoglycerides of variable solubilities.

The combined precipitates of monoglycerides are then dissolved in 1,200 cc. of ethyl alcohol at a. temperature of 60 C., the solution decolditional stages employing, respectively, 1,200 cc., 1,500 cc., 1,400 cc., and 1,200 cc.

The several fractions for the last fractionation were examined and found to be relatively pure materials 'ofvarying unsaturation, free of contaminating substances which cause odor-reversion, color and The monoglyceradmixture for various purposes, particularly as a surface active agent in the preparation of food products, such as ice cream, margarine, short- The polyunsaturated monoglycerides may be steam distilled to remove glycerine, thus yielding an unsaturated triglyceride which may be used as a drying oil. The mono-unsaturated glycerides may be similarly converted to an olive oil type product useful in food products or the like. The triglycerides may be employed for the usual purpose--for example, foods, lubricants or soap or in the preparation of additional quantities of monoglycerides. The diglycerides may be used to prepare triglycerides by steam distillation, or

they may be used in the manufacture of additional monoglycerides.

The fractionation of the mono-esters of different degrees of unsaturation possesses many advantages over the fractionation of the triglycerides because themono-esters contain only one fatty acid radical, either saturated or unsaturated to a definite extent, whereas the .triglycerides include not onlythe fully saturated triglycerides, but also mixed saturated-unsaturated triglycerides, mixed unsaturated triglycerides, and triglycerides of the same unsaturated fatty acids. Obviously it is diflioult, if not impossible, to separate the saturated acid derivatives iromthe various unsaturated acid derivatives in such triglyceride mixtures. The conversion of monoglycerides to triglycerides is much milder than the synthesis of triglycerides from fatty acid and glycerine; hence the resulting oils are not polymerized and are of a better color and odor.

Example [I number and saponification number of 193- is heated with an excess of glycerol in the presence of a small amount of sodium'hydroxide. The soap and excess glycerol are removed by treatment with phosphoric acid after deodorization at about 150 C. The saponification number of the product is 168.0. 30 grams of the product are dissolved in 150 cc. of hot chloroform and 1,000 cc. of hot per cent ethyl alcohol. The mixture is cooled slowly to 2 C. The precipitate which forms is filtered, washed with a little cold alcohol, and dried. The yield is about 5.5 grams of a material having a saponification number of 192, which is substantially the same as the originaltriglyceride material. The solvents are removed from the filtrate. About24 grams of material having a saponification number of 166.5 are recovered. The theoretical saponification number of the monoglycerides is 159.2, and of the diglycerides is 183.3. It is seen that the precipitate from the alcohol-chloroform solution is nearly pure triglyceride, whereas the extract is substantially pure monoglycerides. Additional fractionation of the extract separates the monoglycerides and diglycerides into pure fractions of these materials of varying degrees of unsaturation.

Example III grams of the partial esters similar to those employed in Example II, but with a saponification number of'166 and iodine number of 69.4, are dissolved in 200 cc. of petroleum ether (boil ing point 40-70 C.) and extracted with 250 cc. of furfural at 30 C. in a simple batch extraction. The liquid layers are separated and the solvents removed from each layer by steam distillation in vacuo. The furfural soluble fraction or extract has a saponification number of 155.8 and an iodine number of 67.6. The hydrocarbon soluble fraction or raifinate has a saponification number of 173.6 and an iodine number of 71.6. Some esters of polymerized glycerol are present in the original material and are concentrated in the furfural due to their greater polarity than mono-esters of glycerol; hence the low saponification number. Repeated fractionations of the raiiinate separate the triglycerides and diglycerides, while further fractionation of the extract separates the polyglycerol esters from monoglycerol esters, which in turn are separated into fractions of varying degrees of unsaturation.

The source of the partial esters is immaterial and they may be prepared by any of the methods described in the numerous patents and literature articles. Because of the various sources many different types of admixed agents and impurities are separated by the present process. Among the methods for preparing the materials which may be purified by the method of the present invention are those described in Christensen, U., 16. Patent No. 2,022,494; Edeler et al., U. S. Patents No. 2,206,167 and No. 2,206,168; Kapp, U." S. Patent No. 2,207,251; Oelverweftung, Austrian Patent No. 67,061; and Jurgens, German Patent No. 277,641. This list is merely by way of illustration and the present process is not limited to the purification of the agents prepared by the above processes but may be applied to those prepared by any process. Fatty materials treated in the manner shown in the preceding specific examples and as illustrated in the above patents so as to contain a greater proportion of combined glycerol than ordinary fats, in the form of monoand diglycerides, are referred to as superglycerinated fats or superglycerinated refined fats when the fats are subjected to a preliminary refining operation, and the process of producing the latter as superglycerinating, [The method is effective not only for separating monoglycerides, diglycerides and triglycerides, but also for fractionating mixtures containing one or more of the following materials: Mono-aliphatic acid esters of ethylene glycol, of diethylene glycol, of

diethylene thioglycol, of triethylene glycol, of

1,4 butylene glycol, of 1,2 propylene glycol, of 1,2 pentandiol, or glycerol chlorhydrin, of glyceric acid,of N-diethanolacetamide, of 1,6 hexandiol, and of other glycols; monoand di-organic monocarboxylic acid esters of glycerol, of beta methyl glycerol, of 1,2,5 pentantriol, and of other trihydric alcohols; mono-, di-, triand higher partial esters of erythritol, hexitols, hexoses, and related materials. The acids esterified with the polyhydric alcohol may be any of the organic monocarboxylic acids having at least six carbon atoms, such as caproic acid, n-heptoic acid, caprylic acid, n-nonoic acid, capric acid, n-undecenoic acid, lauric acid, tridecanoic-acid, myr istic acid, palmitic acid, palitoleic acid, elaeo stearic acid, margaric acid, stearic acid, elaidic acid, dichlorstearic acid, oleic acid, linoleic acid, linolenic acid, eicosanoic acid, behenic acid, ricinoleicacid, cerotic acid, melissic acid, acids from oxidized petroleum, naphthenic' acid, abietic acid and/or other monocarboxylic acids, whether cyclic branched or straight chain, saturated or unsaturated, substituted or unsubstituted, or mixtures thereof, such as are obtained from coconut oil, tallow, peanut oil, cottonseed oil,

marine oils, palm oil, olive oil, whale oil, linseed oil, lard oil, castor oil, tung oil, oleo oil, spermaceti, beeswax, corn oil, menhaden oil, perilla oil, oiticica oil, soybean oil, tall oil, and their halogenated and hydrogenated products. The partial ester may be a mixture of the same -'fatty acidesterified to different degrees with different polyhydric alcohols and/or different fatty acids with the same polyhydric alcohol. In most cases it will be a mixture of partial fatty acids of the same polyhydric alcohol, for example monoglycerides and higher glycerides of fatty acidsprepared by reacting glycerine with coconut oil or other fatty oils orfats in the presence of an alkaline catalyst.

in the present invention are. non-reactive polar solvents, preferably organic These. solvents nitrile, acid anhydride, acid amide, carboxyllc ester, aldehyde, ketone, mercaptan, primary amine or primary amine bases, nitro, sulphate, carbonate, and phosphate groups, andyalso may contain one or more of the following groups which assist the above listed functional groups, namely, ether, thioether, olefine, secondary amine and tertiary amine and the corresponding bases. In the case of organic solvents the number of carbon atoms usually should not be greater than six, and the compound may have three carbon atoms for each of the groups listed in the first series, and one carbon atom for any other groups in the compound which are listed in the second series. It is essential that the properties of these materials and the temperatures employed should be such that two phases are formed and that the solvents are not reactive under the treatment conditions. Miscible polar solvent which do not meet the above requirement and also miscible nonpolar solvents may be used in conjunction with the selective polar solvents to be employed in the present process in order to alter the solubility of certain of the constituents under treat: ment. Likewise, it is possible to increase the selectivity of the process by employing non-miscible nonpolar solvents which tend to hold the more fully esterified materials While the polar solvent extracts the less fully esterified more hydrophyllic material. H

The polar solvents which may be employed for the present purposes include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, allyl alcohol, methylallyl alcohol, phenol resorcinol, ethylene glycol, ethylene chlorhydrin, diethylene glycol, diethylene thioglycol, ethylene glycol mono- The extraction solvents which may be employed .bon bisulphide, and the like.

methyl ether, ethylene glycolmonoethyl ether,

. ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol diformate, ethylene glycol monolactate, ethylene glycol monoglycolate, triethylene glycol, propylene glycol, butylene' glycol, 1, 4, pentandiol, pentantriol 1, 2, 5, propylene gly col chlorhydrin, glycerol, glycerol monoacetate. glycerol diacetate, glycerol triacetate, glycerol monobutyrate, glycerol dibutyrate, glycerol monocaproate, glycerol monopropionate, methyl glycolate, ethyl glycolate, ethyl acetoglycola'tje, methyl lactate, ethyl lactate, methyl malon'ate, ethyl oxylate, lactonitrile, propionitrile, methyl allylnitrile, formic acid, acetic acid, acetic anhydride, lactic acid, methyl formate, ethyl formate. methyl levulinate, ethyl 'N -methyl carbamate,

'eth-ylidine diacetate, ethyl acetoacetate, methyl acetoacetate; methylmaleate, methyl furoate, methyl chloracetate, methyl cyanoacetate, acetadehyde, methoxyacetaldehyde, furfuralalcohol, nitrobenzaldehyde, nitromethano, nitroethane, Z-nitro-ethyl propionate, acetone, diacetyl, diacetone alcohol, acetonyl, acetone, formamide, aceta'mide, propionamide, butyramide, N-ethanolac'etamide, aniline, ethyl diamine, diethyl 'triamine, triethylene tetramine,

ethanolamine, diethanolamine, triethanolamine,

monoglycerolamine, diglycerolamine, triglycerol amine, trishydroxymethyl aminomethane, hydroxyethyl ethylene diamine, trimethylphosphate, triethylphosphate, -diethylsulphate, acetylmethylcarbinol, acetochlorhydrin', dichlorotriethylene glycol, 2-hydroxymethyl, 1, 3 dioxolone, methyl butanolone; acetone plussulphur dioxide, liquid sulphur dioxide, liquid carbon dioxide, "car- The temperature ,of. operation as indicated hereinbefore will; depend mainly on ,the method of treatmenh the type of solvent, theproportion ,ofsolvent, and the materialunder treatment, In

attests 11 general, the solvents are more selective at lower temperatures but the quantity of material dissolved is usually lower; hence it is a question of balancing the degree of separation against the quantity of solvent necessary. When liquid: liquid extraction is the desired method, of course a low temperature limit is set by the temperature of solidification of one or both of the phases. A high temperature limit is similarly fixed in most cases by the fact that the polar solvents will either become completely miscible with the total ester mixture under treatment or will dissolve abnormally large quantities of all constituents in the ester mixture. The proportion of solvent to ester material under treatment will usually be within a range of about 1 part to parts by volume of solvent to 1 part of oil. For simple single-stage extractions a .proportion of about 3 to 5 parts of solvent to 1 part of ester material is satisfactory. In counter-current extraction it is, of course, possible to employ smaller quantities of solvent to effect an equivalent purification.

The ester material may be recovered from the solvent solution by crystallization, vacuum distillation, flash distillation, and precipitation .by

the addition of non-solvents such as water. For large scale production it is desirable to recover the solvents for return to the process in the treatment of fresh materials.

As indicated in Example I, the fractional crystallization or precipitation of the partial "esters from the extract solution has the additional merit of removing substances which in many cases have a deleterious action in the extracted product. In some cases these materials will precipitate first from the solvent solution, but in general it has been found that they are among the last materials to be precipitated or crystallized from the extracting solvent. Hence by the processes of this invention it is possible not only to fractionate and purify the partial esters, but also to effect an improvement in color, taste and odor, and the stability of the product in resistance to reversion in these properties.

'The fractionation and purification process may be performedin a single unit with a single solvent, but in many cases there are advantages in operating in several extracting steps of the same type or different types with the same or different solvent or solvents; for example, one solvent may be effective for concentrating the esters of aliphatic polyhydroxy substances of lower degree of substitution when these materials are present in small percentages, but the same solvent may be much less selective when the concentration of the constituent to be extracted .is present in higher proportions. Onthe other hand, another solvent may have a directly 0p- .posite change of selectivity; that is, be more effective in concentratedmixtures than on-dilute mixtures. Hence, when starting with-a material having a low content of slightly esterified materials, the first stage of extraction would be with the former solvent, and theextract of the solvent from the first stage of extraction could then be extracted in a second stage with the latter solvent; In another case, the first stage of extraction may be one involving simple or concurrent mixing and settling to remove a small or large proportion of the constituents of the material under treatment 'followed'by a'countercurrent extraction of the solvent-free extract and/or ofthe raffinate from this first stage of extraction. 'As another'variation, it is possible to obtain an extractor a mixture containing esters of aliphatic polyhydroxy substances in a polar solvent and then to extract'this solution by any method, preferably continuous counter-' current extraction with an immiscible solvent, such as gasoline, petroleum ether or other nonpolar solvents. Any combination of solvents or mixtures of solvents and/ or of methods disclosed herein may be employed in the present process. By non-reactive solvent it is meant to include solvents which do not react with the hydroxy substituted derivatives under the conditions of treatment.

The fractions obtained by these extraction procedures, with or without the solvents present, may be treated with adsorbent agents, such as activated carbon, bauxite, kieselguhr, silica gel and clay, alkali or other purifying agents to yield final products of unusually high purity. Although the above description has been directed to the treatment of partial esters of polyhydroxy compounds, it is likewise applicable to the frac tionation and purification of organic acid amides of aminoalcohols, such as monoethanolamine, diethanolamine, trishydroxy methyl aminomethane, monoglycerolamine, diglycerolamine, and the like. That is, the process is applicable to the esters or amides having free hydroxy groups. The products of the present process may be used wherever the corresponding nonpurified full and partial esters and/or amides have previously been employed. As pointed out in Example I, the agents having free hydroxy groups are exceptionally satisfactory for use as emulsifying agents for emulsifying or for other surface-active purposes. The agents are unusually effective in food preparation, such asvice cream, shortening, peanut butter, and the like, because of their greater efi1ciency, their purity and their greater resistance to reversion. The full esters are likewise improved in color, odor, taste and stability and may be used in foods, lubricants, soap manufacture, manufacture of partial esters, and organic synthesis. The partial esters by themselves possess surface active properties, but for particular purposes these purified compounds may be reacted with inorganic polybasic acids to form the corresponding partial esters thereof, which, when neutralized, are highly desirable surface-active agentspossessing deterging, emulsifying, penetrating and wetting properties.

Another aspect of the invention involves the separation of esters of polyhydric alcohols by solvent crystallization. According to this method the product to be treated is dissolved in the solvent at an elevated temperature and the mixture cooled t precipitate or crystalliz fractions of varying degree of saturation and melting point. The fractions crystallized may then be separated from the solvent by suitable means such as filtration. By reducing the temperature in carefully controlled intervals a plurality of fractions of similar chemical and physical properties may be produced. The .crystallization method is particularly applicable to the treatment of full esters such as triglycerides, but it may be applied to the separation of partial esters or mixtures of full and partial esters by properly selecting the solvent or mixtures of solvents.

When products containing two or more compounds .of the group of monoglycerides, diglycerides and triglycerides are treated, the order'of crystallization from polar solvents is usuallytriglycerides, then .diglycerid'es and then mono- 'glyceri'des. Thus in thejtreatment'of mixtures of -triglycerides, diglycerides and monoglycerides with 'a solvent such as ethyl alcohol andchloroform as described in Example II, the mixture may be separated on reducing the temperature by crystallizationin the reverse order of the number of free hydroxyl groups. In general, the same order applies also to other partial esters. When treating a product comprising essentially full esters as distinguished from partial esters, for example, triglycerides as distinguishedfrom monoglycerides and diglycerides, the order of crystallization is usually according to the degree of saturationandmelting point, i. e., the more saturated'andhigher melting point components crystallize first; l

The crystallization method difiers from the liquid liquid phase operation in that the separation according to the degree of unsaturationis not so pronounced in the crystalization method. On the otherhand the crystallization method gives sharper separation according to the melting point and completeness of saturation and length of carbon chain, whereas the liquid-liquid phase extraction tends to make a separation between "the unsaturated and saturated fractions. Itisfnot possibleby such method to obtain a sharp separation'between products of the same length of carbon chain. c

. m .the, lvent liquid-liquid extraction op erationthe separation is made on differences in V degree' of polarity of the compounds to be separated; Within the class of fatty materials the degree of polarity varies only over a rather narrow range, and it is, therefore, difficult to make asharp separation. On. the other hand, in the solvent crystallization process the separation is made on the basis of the diiference inmelting point and solubility of the various fatty matehas; The melting point varies over quite a wide range, and it is therefore possibletd makequite sharp separations "if the fproperconditions are chosen.

The melting point the degree of solubility to a greater extent than doesthe degree of unsaturation. It 'is, therefore, possible to make a more marked separation on the basis of melting point than on the basis of unsaturation.

To illustrate, attempts have i been made to separate fatty materials on the basisof unsaturation bymeans of solvent crystallization. However, the degree of solubility between the saturated and unsaturated constituents is not sumeiently different to make sharp separations and only a limited number of cuts canbe'made. On the other hand when the separation is made on thebasis of melting point where large differences exist in the degree of solubility, a large number "of cuts can be made, each possessing widely different melting points.

-'-Inthe solvent crystallization process the deg'ree of separation on the basis of melting point can be controlled to some extent by the method in' which the process is carried out. If the crystallization is carried out rapidly, causing a quick crystallization of the higher meltingpoint constituents, some of the lower melting constitue'ntsare likely to be adsorbed or occluded on 'thecrystals, thereby causinga lesser degree. of

final separation. However, if the crystallization is" carried but slowly, and if the solvent ratio and temperature are adjusted, the adsorption and occlusion are held at a minimum. Further, if the crystalsare well formed and granular they can be washed with cold solvent, washing of the fatty material aifects away from themthe lowermelting pointacon stituents which are adsorbed,.resultingina sepe.

aration which is considerably. sharper.

In the solvent extraction process such control Further, the crystallization is not possible. process when applied ina manner to obtain separationon thebasis of melting point as con-.

trasted to that intendedito cause separation on the basis of unsaturation. is; more. easily controlled in that the. crystals are morereadily formed and 18881 occlusion takes place, resulting in a'sharper separation. l

The solvents disclosed aboverinclude which are particularly suitable for liquid-liquid phase treatment and others which are more ap-.

ganic acids; ketones and amines derived. from the lower aliphatic alcohols, and phosphoric:

acid .esters. of lower aliphatic alcohols. The chain length of the acids or alcohols can usually varyiromrl to to about 8 carbon. atoms. .The bestfresults are obtained inthe range of 3.to 5. carbon atoms. In, additionppartially .halo genated derivatives of the above classes oicome pounds can be used. j i Examples of the alcohols are methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohoL; butyl. alcohol, isobutyl. alcohol, secondary butyl alcohol, tertiarybutyl alcohol, amylalcohoLisoe amylflalcohol, allyl alcohol, .methylallyl alcohol; cyclohexanoland methylcyclohexanol. i Examples of esters aremethyl formate, ethyl formate, propyl formate, isopropyl formate, butyl. formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, methyl butyrate ethyl butyrate, propyl butyrate, butyl butyrate, amyl butyrate; ethylene glycol diacetate, ethylene glycol diformate, glycerol diacetate, glycerol triaoetate, glycerol dibutyrate, .methyl furoate, methyl. chloracetate, ethylidine diacetate, and acetyl -methylu.:car=- binol. :i Examples of.,organic acids and organic acid anhydrides, are formic acid, acetic acid, propionic acig, acetic anhydride, butyric acid and .caproic aci I Examples of the aldehydes areformaldehyde, acetaldehy'de, propionic aldehyde, butyl aldehyde andcaprylaldehyde' a m Examples of the ketones are acetone, methyl ethyl ketone, methyl butyl ketone, diethyl ketone, ethyl .propylfketone, dipropyl ketone, propylbutyl ketone, dibutyl ketone, .diacetyl, diacetone-alc0 hol,.acetonyl acetone. V r U Examples of amines are aniline, ethylene diamine, diethylene diamine, pyridine,-- propyl amine, quinoline, butyl amine, amyl amine, and hexyl amine.

Examples of organic phosphates are ethyl phosphate, diethyl phosphate, propyl phosphate, dipropyl phosphate, butyl phosphate, dibutyl phosphate, ethyl-butyl phosphate, ethyl. propyl phosphate, propyl butylphosphate, triethylphosphate, tripropylphosphate and tributylphosphate. Examples of chlorinated products are methylchloroformate, methylchloroacetate,dichloro tri- 15 ethylene glycol, beta-beta. .dichloro ethyl, ether and ethylene dichloride.

Examples of ethers are methyl ether, ethyl.

ether, ropyl other, isopropyl ether, butyl ether andamyl ether.

I It may be desirable. in some cases to use mixtures of two or more. of: the above solvents.

Instead of chilling the mixture of solvent and ester of polyhydric alcohol. in. order to cause crystallization, an antisolvent may be added. The

antisolvent'is a materialin which fats are insoluble or only slightlysoluble. They may be polar, low'molecular weight compounds. The most common are water and the lower aliphatic alcohols such as'methyl and ethyl alcohol. The temperature at which they. are used will vary, depending upon the fat solvent which is used, and the type of vfatty material which. is in solution. At times it is advantageous to use a combination of cooling and the antisolvent. Itis generally necessary to add the antisolvent rather slowly and with quite rapid agitation in order to produce a precipitate which is crystalline and easily filterable.

In practicing the invention. the fat and crystallization solvent may be fed in properly proportioned amounts to a chiller wherein the mixture is chilled'to cause separation of crystallized fractions. The chilled mixture may be mixed wlthadditional cold solvent and the'product sub- .iected to filtration in a rotary continuous type of filter in which the solid material is removed as-a filter, cake on a segmented rotating drum. The filter cake may-be washed by a portion of the scold solvent and the used wash solvent may be reused in the system; for example, by mixing it with thecharge to the filter. The solvent may be: stripped from the filter cake and the filtrate in suitable strippers.

.;The lower .molecularweight alcohols, methyl, ethyl, and isopropyl alcohol, are not generally suited for use as solvents in the crystallization of triglyceride fattymaterials or for completely esterified esters of other polyhydric compounds without the use of auxiliarysolvents. If the fatty compounds contain unesterified hydroxyl groups such. as in the case of monoand diglycerides, then thelower alcohols find utility. The polar nature. of .the molecule of the fatty material is increased if it contains free hydroxyl groups, and thelowteralcohols, being polar in nature, naturally dissolve the partial esters quite readily. The completely esterified esters of glycerol and other polyhydric alcohols, such as triglycerides, being non-polar innature are not soluble to an extent in the'lower alcohols alone to render them practical as solvents for crystallization. As the chain lengthincreases in-ithe alcohol, the solubility of the completely esterified esters increases and their application as solvents for crystallization increases. Normal propyl alceholcanbe used with a fat of intermediate hardnesssuch-as lard, cottonseed oil, tallow, grease and partially hydrogenated oils, etc.

' Generally, the softer the fatty material used, the smaller the amount of the solvent required to cause complete solution at elevated temperatures. As the melting point of the, original fatty material increases, more solvent is necessary in order to obtain complete solution. Generally, for thecommon fatty materials, such as inedible greases and soybean oil from one-half to five volumesand preferably one to three volumes of solventtoone volume of oil'suffices. However, with .the..more saturated higher melting point fatty materials such as tallow and substantially completely hydrogenated fats or oils considerably.

more solvent may be necessary, for example .up to ten volumes of solvent to one of fat.

The temperature of solution also depends on the solvent used and the melting point of the fatty material. For example, normal propyl .alcohol dissolves an equal volume of lard at 100 F. Normal butyl alcohol dissolves an equal volume of lard at F., while normal amyl alcohol dissolves lardat room temperature. As the chain length of the alcohol increases,.- solution is obtained at a lower temperature. Generally, tem peratures from room temperature (about 0 F.) to F. are satisfactory. However, temperatures up to the boiling point of the alcohol may be necessary in order to obtain complete solution with the higher melting fats such as tallow and.

*" with the alcohol used and the type of fatty maerial dissolved. The higher the melting, point of the. fatty material used, the higher will be the temperature 7 at which crystallization begins. Over-all temperatures within the range of 10.0 F. down to 0 F. will generally be satisfactory.

It was'pointedout above that ethyl, methyl and isopropyl alcohols are not suitable for the crystallization of triglyceride :fatty materials. How ever, if an auxiliary solvent is used with them, a sufficient solubility. of the triglyceride material is obtained so that crystallization can-be carried out. 7

In the case of triglyceride fats, when the lower. molecular weight alcohols are used the auxiliary solvent will be non-polar innature. For example, a mixture of ethyl alcohol and diethyl ether can be used for crystallizing such as destearinating triglyceride materials such as cottonseed-oil or tallow.

With the triglyceride fatty materials an alcohol of lower chain length may be used if an auxiliary solvent is employed. For example, .normal propyl alcohol can be used for the destearination of lard while ethyl alcohol is not particularly suitable. However, if a mixture of ethyl alcohol and isopropyl ether is. used, suflicient solubility is obtained so that the destea-rination process can be practical. 1

In the separation. of .mono-, diand trlglycerides, usingthe lower alcohols as a crystallization solvent,- sometimes it is advantageous touse an auxiliary solvent; A smaller amount of alcohol can be used and crystallization can be carried out ata lower temperature. Also, it is possible to-obtaina bettertype of crystals. Even at times it is possible to obtain separation of crystals instead ofoilS.

However, in the case of partial esters of polyhyclric alcohols, the lower alcohols such as methyl and ethyl alone can be employed, but the ratio of solvent and the rate of cooling must be carefully adjusted inor-der to avoid separation of oils and in order to obtain a sharp degree. of. separation.

.'.When using'an auxiliary solvent the sepae ration of mono-, di-qand triglycerides the temperature at which the triglycerides separate is below their melting point, and therefore they crystallize'in we'll-formed crystals. However, if the auxiliary solvent is not employed, separation of the triglyceride material is at-a temperature which is generallya-bove the melting point of the o Separation of oils generally gives a less sharp oilfromthe solution, fairly good separationis obtained. a

e The separation of crystals is much easier to accomplish on a practical scale than is the separation' of oily materials. The crystals can be washed with pure solvent, resulting in a sharper degree of separation.

If the ratio of solvent to the mixture of mono-, diand triglyceridesis controlled so that the triglycerides separate at a temperature below their melting point, then crystallization will be obtained The latter will require considerably more solvent than in the case where the oily material separates, and it is necessary to carry out the chilling at a slower rate.

Example IV An equal weight mixture of monoand trilaurin was dissolved in four volumes of ethyl alcohol at about the boiling point of the alcohol. Thesolution was cooled slowly to room temperature and the precipitate separated Was filtered arid washedrwith a smallquantity of ethyl alcohol at room temperature. The melting point of the precipitate was 58 C., the melting point of the filtrate was 52 0., and the melting point of the original mixture was about 48. About per cent'of the original material appeared in the precipitate and consisted essentially of trilaurin.

The filtrate was chilled slowly to about 2 C. and

the crystals which separated were filtered and washed'with coldethyl alcohol. Their meltin point was about 58 and the sum of the two precipitates (trilaurin) made up about 50 per cent of the original mixture.

Example V Example VI Prime steam lard was dissolved in an equal volumeof normal capryl alcoholat 100 F. The

solution was cooled to about F. and filtered by gravity and washed on the filter with a small quantity of chilled capryl alcohol. The precipitate amounting to 10. per cent of the original lard and containing tristearin had a melting point of 125 and the filtrate had a melting point of F. The melting pointlof the originallard was about 110 F.

All fatty materials are quite readily soluble in the ketonesn The solubility of the fatty material increases with the chain length of the ketone s, but those containing from 3 to 6 carbon atoms are best adapted for crystallization. The fatty materials generally crystallize in granular crystals from this class of solvents. The amount of solvent required varies, depending upon the molecular weight and melting point of the fatty material. Generally, one-half to five volumes of solvent forkone volume of fatty material is required. However, there may be cases whereup to ten volumes of the ketone. may be] necessary. 'lhe temperature required for solution is gen.- erally quite low, approximatmg the rangelrrom room tempei'atureto 1F/ However... in the case of the lower molecular weightlretories'hrid the higher melting .point fatty' materiaigconsiueracly higher temperatures up. to the boiling point of the Keytones may be required in order to obtain complete solution. Ketones can be used to dissolve both completely. esterified and partial esters of .polyliydric alconols and are suitable for crystallization of either types of fatty materials. f

Ed/ample v11 A sample of white grease was dissolved in an equal volume of acetone atroom temperature and chilled under agitation to about 40 F. "l'hemix ture was then filtered through a vacuum 'filter using a canvas covering as the filtering surface. After filtration was completed the precipitate containing essentially the glycerides of stearic and palmitic acids was washed on the filter with a small quantity of acetone at about 40 The solventwas removed from both the filtrat'e' and the precipitate by vacuum distillation. The fraction which precipitated consisted of about 20 percent of the original weight of the grease and had a' melting point of about 50 C. and an iodine number or about20. Thefiltratehad a rieltirrg point of about 30; C. and an iodine numberj o'f about 75. l l i i f Example VIII-f Refined and bleached cottonseed oil weredissolved in an equal volumeofimethyl ethyl ketdne at 100 F. andchilled under agitation toab'out 40F. The mixture was filtered by means eta vacuum and the precipitate washed with a Ismall quantity of chilled solvent. The solvent was re moved from both the filtrate and precipitate by vacuum distillation. The precipitate containing the glycerides of the more saturated fatty acids consisted of about 20 per cent of the originaljoil and had an iodine number of I02 and a melting point of 75 R, and th'e filtrate had'aniodine number of 112 and acold test of. about 30hours and a melting point of 30F. It willbe observed that'the separation was made on thebasis .of melting point in preference to separation on the basis of unsaturation.

Example IX Refined and bleached cottonseed oil were dissolved in an equal volume of-methyl butyl ketone at room temperature and the -solutiori emanate about '27" F. over a period of two-hours. Then 50000; of methyl butyl ketone were-addd-and the mixture filtered through a vacuurn filter using a canvas. covering as the filtering surface; The precipitate containing the higher melting glycerides'of cottonseed oil was washed on the filter with a small quantity of methyl butyl ketone at about 30 F. The solvent'wasremoved from the precipitate and filtrate. The oil infthe filtrate consisted of about 72 per cent of the original oil and had'an' iodine number. of -111,a pour point of 10 F. and acoldtestof "19 hours.- The stearin or precipitate fraction had a titer of 42.2 and an iodine number of 89. The latter consisted of about 28 percent of the original oil.

Fats including partially or completely esterified materials are soluble in all proportions esters, even those of lower molecular weight. However, the solubility of the fat in this class of solvents asset-a 19 increases as the chain length of the esters increases. V The solubility of thefattymaterials' in these esters 'decreasessomewhat as the melting pointpf' the fatty material "increases, "and 'the "de'greeof saturation increases. With most of the common'fatty materials, one-half to five volumes ofsolvent is sufficient to "dissolve the'fatty material, but with the higher melting point fatty materials considerably'more solvent may be required, particularly if lower molecular weight *estersare 'used as thesolvent. Generally, temperatures'fromroom' temperature to 100F. are all that is required to obtain complete solution. However, it" may be necessary in the'case' of "the higher melting fatty materials to use a higher temperature; for exampleyup'to 200 F. or over. Eats and fatty materials crystallize from the esters at temperatures varying with the type of fatty material and the ester used, as well as the Quantity of ester .Generally, temperatures of the range from 100 F. down to F. will cause precipitation of at least the higher melting point iraction of the fatty material. However, in order 19. -.1 precipitate,, completely, the low molecular weight, W melting point fatty materials, it may be necessary to. use temperatures considerably under 01 Example 'X lie'fi nedand bleached cottonseed oil was mixed with about an equal volume of methyl formate, passed through a tubular chiller, and chilled to a temperature of about 30 F. About one-half part by volume of methyl formate was added to the chilled mixture and thewhole mass passed through a-continuous rotary vacuum filter which was equipped for Washing the precipitate which gathered on the' rotarydrum'. The precipitate consisting essentially *of cottonseed stearin was washed with a"small"portion of methyl formate at ZiO" F. The precipitate was scraped from the drum and the solvent removed by distillation. Tneprecipitateconsisted of about 30 per cent by weight "of the"original oil,' and had an iodine number of about 106and a melting point of about 903?; The filtratewaspassed through a solventfrecovervsystem, and after the solvent had been removed it had'aniodine number of about 115 and a cold test .of' about 10 hours (which means that a sample placed in 'a four-ounce glass bottleand put in an ice bath will show no cloudiness until after 10 hours).

Example XI choice white grease was dissolved in. anequal volume of ethyl formate and the'solution chilled to 45 5'. over a period, of about 75 minutes. Chilled ethyl formate was added and the mixture filtered by means of a vacuum filter, using a; canvas covering. as the filtering surface. The precipitate o; f stearin was washed with a small quantityof chilled solvent, and the solvent was removed from boththe' filtrate and precipitate byvacuum distillation. The filtrate had a pour point: of about 3551. and an iodine number of about 72. Theprecipitate amounted to about 20 per cent and had an iodine number of about 46yand a titer of about 113 F.

Example XII Neats-foot oil was dissolved in an equal volume of methy'l chloroaceta-te at room temperature and the solution chilled to"30 F. The precipitate containing the glycerides of the higher melting pains acids was'filtered by ordinary gravity filtration andwashed was small quantity ofjthe solvent. The solve'ntwas removedffrom the-{filtrate and the precipitate by heating mava uum. AboutZO per cent ofthe'original' 'oilwas pres t in the precipitate, which' had' atiterof iabout F. 'an'd'a pour point of 'about40? F. The file trate consisting of the remaining '80 per cent of the oil had a pour point of 15 F.

'Ethers readily dissolve completely 'esteri'fied esters of polyhydric alcoholsbecauseoffthe onpolar nature of the two types of compounds. However, ethers 'do'not readily dissolve'pa'rtial esters of polyhydric alcohols bec ausethe latter are polar- The'fdegree of"solubili'ty' dependsbn the amount of polarity. For example; trilauri'n is'easily soluble in ethyl ethe 'monolaurmjis quite insoluble; and dilaurin of intermediate solubility. Forlthe' common triglyceride :fatty materials only relatively small volumes of ethers are required, one-half to fivevolu'r'n eslu sually sufficing. However, if the 'fatty material is of high melting point, moreether is required; for example, up to ten volumes or'more. The temperatures required for solution of'the common fats are quite low, ranging from room tempera-.

ture to F. However, if the fatty material is of high melting point, temperaturesup 'tocthe boiling point of the ether may be required. The fats crystallize from the ethers at quite. low tem-'- peratures, from room temperature down to -40 F.

When ethers are used onpartial esters of polyhydric alcohols, an auxiliary solvent which is'polar in nature is required. For example, a mixture of mono di-, and triglyceride ofpartially hydrogenated "cottonseed oil maybe dissolved ina mixture of propyl ether'andpropyl alcohol and crystallization of the tri-, anddi glycerides obtained when'the solution is chilled.

ExdmpZaXHI An 80-20 mixture of triolein and trilaurin was dissolved in three volumes of ethyl ether at about the boiling point, and the solution cooled to 40 F. The crystalline precipitate which separated was filtered and washedwith cold ether and the solvent was'removed fromthe'filtrate and precipitate by-heating in a vacuum. The precipitate, which consisted of trilaurinf and amounted to 15 per cent of the total, hada melt ing point of 113 F. The filtrate'had' am'lting point of40 F.

Example XIV Prime steam lard was dissolved in an equal volume of isopropyl etherat Fi'and the-mixture slowly cooled to 40F. The flufiy precipi= tate which separated was filtered and washed with cold isopropyll'etlier. The solvent was-re: moved from the filtrate and precipitate and their melting points determined. The precipitate which consisted essentially of the glycerides of palmitic and stearic acids ha'd'a melting; pointof about 118 F. The filtratemelted at about 43 F;

solution chilledto 40 Runder agitation. The

precipitate was filtered by means of "a'vacuum using a canvas as the filter medium. Theprecipitate was washed with cold solventjand' the solvent removed fromboththe filtrate 'an 'd lp {$2 cipitate byheatingidvacrio. The precipitate which contained glycerides ofthe higher melting fatty acids and. amounted to about 30 per cent of the original oil had an. iodine value of about 118, andthe filtrate an iodine value of about 106.

Fatty materials crystallize from the lower alkyl esters of phosphoric acid in well-formed, easily filterable crystals. Both the partial and fully esterified esters of polyhydric alcohols are soluble in the organic phosphates. With the ordinary fats such as cottonseed oil, greases, and lard, onehalf to five volumes of solvent per volume of fatty material is sufiicient. If the fatty material is of high melting poinirmore solvent may be required up to ten volumes or more. Temperae tures from room temperature (70 F.) to 200 F. are sufficient to obtain complete solution. Crystallization takes place at room temperatures F, depending on the amount of ester and the melting point of the fatty material.

7 Example XVI Glycerlnated hydrogenated cottonseed oil of iodine number of about 80 was dissolved in two volumesof ethyl phosphate and the mixture was cooled to 35-1F; The solid materialwhich separatedwas filtered and washed with cold ethyl phosphatej Thesolventwas removedby vacuum distillation and iodine values determined on the filtrate and precipitate. The precipitate had an iodine value of about 84, and the filtrate an iodine value of about 77. The precipitate consisted essentially of completely esterified glycerol esters and'm'ade up about 20 percent of the original charge. H

Example XVII An equalvolume'mixture' of white grease and propyl phosphate was made at 100 F. and the solution cooled to 40 F. The solid material which separated was filtered by means of a vacuum and washed with cold solvent. The precipitate had a titer of about 109 F. and the filtrate a melting point of 40 F. The precipitate contained about 22 per cent of the original grease and consisted essentially of the glycerides of the higher melting fatty acids of the grease.

Example XV III Refinedsoybean oil of iodine value of 130 was dissolved in one volume of butyl phosphate and the solution cooled to about 35 F. The precipitate after filtration and removal of solvent had mmame value ofabout 120, and the filtrate an iodineyalue ofabout 135 after removal of the solvent."- The precipitate contained about 40 per cent of the original oil and consisted of the higher melting glycerides.

The ester material may be recovered from the solvent solution by crystallization, vacuum distillation, flash distillation, or precipitation by the addition of non-solvents such as water. For large scale production it is desirable to recover the solvents for return to the process in the treatment of fresh materials.

Thefractionalcrystallization or precipitation ofthe esters from the solution may be used to remove substances which in many cases have a deleterious action in the product. In some cases these materials may be precipitated first from thesolvent solution, or they may be among the last materials to be precipitated or crystallized from the heated solvent. Hence, by the processes of this invention it is possible not only to fractlonate and purify the esters, but also to effect an improvement in color. taste and odor, and the 22 stability of theproduct in resistance to reversionln these properties. U Q

1 l The color, flavor, stability and reversiongc'aus ing materials in fats is due to the-presence of compounds of quite different chemical nature from the fats themselves. Their solubilities are also different, and by the use of the proper solvent and temperature it is possible to separate them from the fatty materials. For example, the com; poundsin soybean oil whichcause reversion, may be separated from the oil by converting the hydrogenated oil to monoglycerides and crystalliz'-- than the fats and, therefore, may be separated under proper conditions. In the caseswhere the color-forming bodies are less soluble than the fats, they precipitate at a higher temperature than the fats. However, in most cases the color-forming bodies are more soluble than the fats and remain in solution after the fats have been precipitated. vAn example of the latter is the separation of the colors of soybean oil by crystallization from acetone; If soybean oil is dissolved in acetone and repeatedly crystallized, a water-white oil is finallyobtained and the color remains in the solvent. I

The. fractions obtained by crystallization with or without the solvents present maybe treated with adsorbent agents such as activated carbon, bauxite, kieselguhr, silica gel, and clay, alkali or other purifying agents to yield final products of unusually high purity. j

Obviously, many modifications and variations of the invention hereinbefore set forth' may be made without distinguishing from the spirit and scope thereof, and therefore only such limita-- tions should be imposed as are indicated in the appended claims. i j

This application is a divisional application of applicants co-pending application Serial No. 567,126, filed December '7, 1944, which matured into Patent No. 2,553,288 on May 5, 1951, which, in turn, is a continuation-in-part of Serial No. 378,063, filed February 8, 1941, which was abandoned, which inturn is a continuation-in-part or Serial No. 267,906, filed April 14, 1939, which matured into Patent No. 2,308,848 on Januarydi), 1943. Weclaim: l. A process for the separation or higher fatty acid partial esters of polyhydric alcohols into fractions having substantially uniform chemical and physical properties, which comprises?" ad mixing higher fatty acidesters containing substantial amounts of higher fatty acid .partial esters of a polyhydric alcohol with from V to 15 parts by volume of an ester of a lower aliphatic alcohol and an aliphatic monocarboxylic acid at a temperature between 70 F. and 200 F. to ob tain a complete solution of the saidfatty acid esters, then cooling said solution stepwise at small intervals of temperature between about F. and -40 F. and separating the distinct phases formed after each stepwise cooling operation, whereby several higher fatty acid partial esters having s'utstantianyiii'ri"rorm-eheniicaiand physical properties are obtained." Y h r -21 A'prooes'sgfor the-separationpf h flier fa'tty acid pa-itial esters "of polyhydric alcohols into fracti ons having substantial-1y iiniform chemical and physical properties, which comprises: adm'ixi'ng higher fatty .acidesters containing 's'ulo- "stantial "amounts of 5 higher fatty acid "partial esters 'of polyhydricalcohols with h from 2/ to '15 parts by volume of an ester of a lower aliphatic alcohol and an aliphaticffinonocarboiiylicfacid "at atemper'ature' betw'een lofl and 200F5' to obtain a completesolutionof the said 'fatty acid esters, then cooling 'said I soliitionstepwis'e' at small intervals cf-temperature between" abbht 1 00*F. and :F andseparatii'ig the distinct phases formed after each stepwi'se -cooling 10p;- elatioh', whereby isever alhighei fatty acid partial 'e'st'ers "having silhstailtlaliy "u iform chemical and physical properties are obtained.

3. Aproeess'sub stantially as deshribedinclaim Q2Whereinthe 'es'ter employed as the" "solvent for the 'ifatty'material is 'methyl formate. v

' 4. A'process substantially asdescribedincl'aim 2 wherein the ester employedas the solvent "for the "fatty" materm "is ethyl acetate.

5 'procefss'fsubstantiallyas described in claim 2*wherein the esteremployed as the solvent for the fatty materialfis isopropyl acetate.

f6 process substantially as described in claim Z'Wherein theester'employed 'as the solvent rer the fattymaterial isethyl formats. 7

V 1 7. A process substantially as described in claim 2 'wherein' the esterlemployeda's the solvent for the fatty material is methyl chloroacetate.

8. The method of purifying partial gly'oerides formed bysuperglycerinating refined fats to sepetherefrom"materials tending to cause reversion 'of"flavbr and odor, which comprises treating" a supergly'c'erinated refined f at containing'siihstah'tialarhounts of'pa'rtial glycerid'esvvith an ester of a lower aliphatic alcohol and an aliphatic"monocarboxyue acid as the solvent at a" temperature "at which thepartial glyc'erides and'frversion-eausing materialfdi'ssolve in the ster solvefit, cooling the solution to precipitate the paftial"g'lycerides; and separating the same precipitate from the solution of reversioh eausmet-laterals. 1 I

9. The method "ofp1irifying' monog'lycerides fo'rh'idhy 'siiperg lyoerihating refined rats to "sepeererrommatenns tenqmg 'to cause rever- 's"1o o flavor-and "odor; which comprises' treatiii'g a. sueergiycerm'ated refined fat containing 9"wherei-n"the ester employed as the solvent for thefa'tty 'r'riixto'r'e is methyl formate.

"11.-A' process substantially as described in claim awiieremthe ester employed as the solvent for the fatty hd iiitiir e isethyl acetate.

12'.Afp'rocess siibs'tantially as described'in claim g'whfeiil the ester e'mpIoyed as the SOIVeht for the FIfattyTii'iiXtfire is isoprop'yl acetate I ISYA iii' OGS S substantially aS describedih Claim 11 (ix-wherein the esterwemployedias the-solve 2'4 s-"wrlerein the ester eniplhyed as' the solverit fof thef attyin'iir'tiire is ethyl-inmate;

14." A' process 'sulistantially as desoribed' in' 'claiin 9 wfhereih 'the ester employed as 'th'SOlVfit-fbi the fatty miXtili'is methyl chloroaoetate' 15.'A process-- for the maniifactu're of partial glyceride es'ters of'a fatty acid-'whicha-re rec of flavor and-odor, comprising 'siib jeb'ti-i'1g"a-;-ie fined glyceride fat which-has been hydrogenated and treated-with glycerine-to'convert said fat into a mixture containing-a substantial proportiohof partial glycerides to solvent-treatment"with -an esterof a 'loweraliphatic alcohol and an'aliphatic monoca-rboxylic acid at atemperature" at which a single liquid phase is formed; reducing the tentperature so that two distinct phases {are formed, one of said phases comprising a' solution of-the solvent and thematerial tending to "cause reversion of flavor and'o dor and the other phase-cam prising the partial glycerides,-- and recovering the partial glycerides free of reversion-causing mae v 161A process for the 'manilfaetu'reof" riiohoe glyceridee'sters'of a fatty acid which are'freeoi flavor and odor, loomprising subjecting a refined glyceride fat which has been hydrogenated' aiid treated with glyc'erine to "convert said" fat'iinto a mixturefcontaining a substantial proportiori'of monoglycelri'des to solvent treatment 'with an ester of a lower aliphatic alcohol and an aliphatic'mfonoc'arboxylic acid at a' temperature at Whicha single liquid phase is form'ed,'redi1cirig the item'- peram'reso that two distinct phases are formed, one of said phases comprising a solutionhftlie solvent and the material tending to cause reversion of flavor and odor and the other phase comprising the monoglycerides free of reversion,- c ausing;material, and recovering the monog'ly c erides free of reversion-causing material. I l7. Aprocesssubstantially as described in claim 15 wherein the ester employed as the solvent for the-fatty mixture ismethylformate. a I 18; A process substantially as-described-inclaim l6 wherein the ester employed as thesolvent-for the fatty mixture fis ethyl acetate H 19. A process substantially ascdescribed in claim 16 wherein the ester *mployed'as the solvent for the fatty mixture; is isoprojpyl "acetate;

zeta-process substantially as describedinolaim '15 wherein-the, ester;employed as thersoivent-rfor the fatty mixture, is .ethxrlformataei; W

121-. Aprocess substantial-1y asidesoribedn claim the fatty'mixturesis'methyllchloroacetate; HARnAND-H.-.Y0UNG C-.=BL1ACK.

f j" The following references are of recorddn-i-the file of this patent: p '5 UNIT-E 13 sT *-rEs-l=ATENTs f i j Niiniher 'Name 

1. A PROCESS FOR THE SEPARATION OF HIGHER FATTY ACID PARTIAL ESTERS OF POLYHYDRIC ALCOHOLS INTO FRACTIONS HAVING SUBSTANTIALLY UNIFORM CHEMICAL AND PHYSICAL PROPERITIES, WHICH COMPRISES: ADMIXING HIGHER FATTY ACIDS ESTER CONTAINING SUBSTANTIAL AMOUNTS OF HIGHER FATTY ACID PARTIAL ESTERS OF A POLYDRIC ALCOHOL WITH FROM 1/2 TO 15 PARTS BY VOLUME OF AN ESTER OF A LOWER ALIPHATIC ALCOHOL AND AN ALIPHATIC MONOCARBOXYLIC ACID AT A TEMPERATURE BETWEEN 70* F. AND 200* F. TO OBTAIN A COMPLETE SOLUTION OF THE SAID FATTY ACID ESTERS, THEN COOLING SAID SOLUTION STEPWISE AT SMALL INTERVALS OF TEMPERATURE BETWEEN ABOUT 100* F. AND -40* F. AND SEPARATING THE DISTINCT PHASES FORMED AFTER EACH STEPWISE CCOOLING OPERATION, WHEREBY SEVERAL HIGHER FATTY ACID PARTIAL ESTERS HAVING SUBSTANTIAL UNIFORM CHEMICAL AND PHYSICAL PROPERTIES ARE OBTAINED. 